Fractionation of gases with solid adsorbents



Patented Sept. 19, 1950 UNITED STATES PATENT OFFICE FRACTIONATION OF GASES WITH SOLID ADSORBENTS Harold W. Scheeline, East Orange, N. J asaiznor to Standard Oil Development Company, a corporation of Delaware Application December 17, 1948, Serial No. 65,943 6 Claims. (Cl. 183-114.2)

This invention relates to improvements in the art of fractionating mixtures by countercurrent contact of mixed vapors with moving fluidized masses of solid adsorbent particles. It applies especially to the fractionation of gaseous or vaporous mixtures of hydrocarbons.

The fractionation of a gaseous mixture by causing it to flow upwardly through an adsorption zone where it contacts a fluidized adsorbent material such as silica gel or carbon in small particle or powdered form which is passed downwardly through this zone has been already described. The adsorbent leaving the bottom of the is then cooled and returned to the top of the adsorption zone for re-use.

In such operation the adsorbent can be caused to exercise highly selective action in removing more readily adsorbed materials, such as hydrocarbons of higher boiling point, substantialLy completely from mixtures containing less readily pressure and the gas composition in contact with the solid adsorbent thus tends to approach an equilibrium concentration for each adsorbed ordinary conditions, if both types of compounds have been adsorbed, the separation of the more volatile and less volatile homologs.

An object of the present invention is to provide an improved process and apparatus for accomplishing such separation of intermediate fractions in a state or high purity by means of a solid adsorbent from mixtures 10 intermediate component fractions.

According to the terms of this invention the means of granular activated carbon.

In the fractionation process the hydrocarbon feed gas is passed under pressure of about 30 p. s. i. g. into an intermediate point of an adsorption tower. Activated charcoal of approxifluidized dense bed countercurrent to the upfiowing hydrocarbon gas. The tower contains perforated plates or other stage-producing devices combined steaming and heating serve to strip the adsorbed gases, part of which are removed as product via cyclones from the disengaging section of the tower-and part being refluxed up the column. The hot stripped charcoal from the bottom of the heater is conducted upwardly by the action of high velocity recycled overhead lift gas which is repressured by suitable blowers. The hot charcoal is cooled by passage through one or more suitable cooling stages and is then ready for another cycle of the adsorption process.

Suitable apparatus for use in this process is shown diagrammatically in the attached drawing. The figure is a view in sectional elevation of one type of apparatus adapted to carry out the process of the invention.

Referring to the drawing, numeral I represents a primary adsorption tower which is divided into an uppermost disengaging section 1, an adsorber section 2 located above the feedpoint 5, a rectifier section 3, directly below the feed-point, and a desorber section 4 below the rectifier section. A feed gas which for purposes of example may be a mixture of hydrogen, methhydrocarbons, C3+ hydrocarbons and inerts is introduced into the primary adsorber tower via line 5 at a point between the adsorber section and the rectifier section. A fluidized mass of adsorbent, the source of which will be described, is allowed to pass downwardly through the plates of the adsorption tower on which the adsorbent reaches a level indicated by the numeral 8. The fluidized adsorbent is introduced into the top of the adsorber at a temperature of about 400 F. to 500 F. In its passage down through the adsorber section of the tower, the adsorbent is cooled by a series of cooling units located on the successive trays of the tower so that by the time the fluidized adsorbent reaches the feed-point, it has been cooled down to a temperature in the neighborhood of 100 F. to 200 F., preferably about 150 F.-l70 F. The fluidized adsorbent passes down the tower at such a rate that substantially all the C2 and heavier hydrocarbons are selectively adsorbed on the adsorbent within the adsorber section while the methane, nitrogen and lighter components pass overhead through line Ill into cyclone II and out through line l3. Entrained adsorbent is returned to the tower via dip leg l2.

The adsorbent passes down the tower into the rectifier or enriching section 3 below the feedpoint wherein equilibrium is brought about between the methane, nitrogen and the lighter gases which may have been adsorbed and the C2+ hydrocarbons by refluxing the enriched adsorbent with C2+ hydrocarbons which have been desorbed from the adsorbent at a point within the desorber section 4. 3, therefore, any nitrogen, methane or lighter gases which may have remained on the adsorbent as it passes down through the tower are desorbed by the action of the refluxed C2+ hydrocarbons due to the more selective action of the adsorbent for the heavier hydrocarbons. The

' nitrogen, methane and lighter material flow upwardly through the rectifier into the adsorber section and are withdrawn from the system via line H]. A number of rectifier zones may seemployed depending upon the number of streams of-hydrocarbons of different molecular weights which are to be obtained from the desorption action.

In the lower section of the rectifier zone the adsorbent is refluxed with the heavier components of the hydrocarbon feed, for example, the C3+ hydrocarbons whereby the desorption of the C2 hydrocarbons is brought about. The C2 hydrocarbons are removed in controlled amounts as In the upper part of section and has adsorbed on it only cyclones to a quench a vapor stream from a point near the center of the rectifier zone via line l1 and introduced into an external sidestream adsorber Hi to an upper section of which is fed a controlled amount of a fluidized mass of adsorbent via line l6 from the adsorber section of the primary adsorption tower. The sidestream adsorber is similar in construction to the primary tower but is smaller in diameter and has fewer trays. The adsorbent stream is substantially free of 03+ constituents the Cl, C2 and lighter materials. The C2 vapor sidestream entering the bottom of the sidestream adsorber is passed countercurrently to the solid stream. By properly controlling the flow of vapor and the fiow of solid adsorbent to the tower a substantially pure C2 out can be withdrawn via line H! as a vapor product from a plate near the center of the tower. In the upper part of the sidestream adsorber the solid is stripped free of methane and lighter components while in the lower part the solid adsorbs the C3 and C4 components from the upfiowing vapor. The vapor stream leaving the top of the tower via line l9 contains some C2 hydrocarbons but consists substantially of methane and lighter materials and is re-introduced into the adsorber section of the primary adsorption tower. The solid stream leaving the sidestream adsorber is introduced via line 20 into the rectifier section of the primary adsorption tower. Thus the sidestream adsorber is supplied with a stripping section for the removal of methane and lighter materials from the C2 intermediate cut. However, the rectifier of the primary adsorption tower performs the operation of rectifying the C3+ stream from the sidestream tower. The intermediate heart out withdrawn from the sidestream adsorber via line I8 is passed through appropriate cyclones for separation of entrained solids therefrom and thence to a scrubber for final clean-up. The latter equipment is conventional in the art and is not shown in the diagram.

Returning to the desorber section of the primary adsorption tower, the adsorbent, substantially free of C2 and lighter gases, passes from the rectifier section 3 into the desorber section 4. In this section desorption of the C3 hydrocarbons is accomplished by means of heat supplied to the enriched adsorbent by suitable heating means such as condensation of high boiling liquid, hot fiue gas, etc., illustrated by units 2| located within the trays of the desorber section. The action of the heat together with steam disengages the 03+ hydrocarbons from the adsorbent and they pass upwardly through the desorber section. Steam is added to the bottom of the desorber section via line 22. Additional steam is formed from the vaporization of water contained in the charcoal slurry entering the desorber section via line 35. Theadsorbent slurry emanates from the tail gas scrubber, the C2 quench tower as will be explained later. Passing up through the desorber therefore are the Ca+ hydrocarbons and water vapor which are removed in part via line 23 and led through appropriate tower to knock out steam and to scrub out any adsorbent material of small particle size which may have passed through the cyclones.

The lean or stripped adsorbent is removed from the primary tower via line 24 and valve 25 and is returned via lines 6 and I3 by the action of high velocity lift gas repressured by blower 34. The charcoal passes through gas lift line B and is inproduct scrubber and the Ca .tion of the lift gas is troduced into the gas-solid disengaging section I wherein the bulk of the solid separates from the The lift gas passes out the tower via lines i and i3 after passing through cyclone II. The cyclone serves to remove the bulk of the entrained solid of any appreciable size which solid is returned to the tower via dip leg l2. A porremoved from line is via line 26 and is employed to lift make-up adsorbent from storage drum'z'l via line 28 and valve 29 into the gas lift line 6. p

The tail gas emerging from the tion tower via line I3 is removed in part via line a tail gas scrubber where the remaining entrained solids of fine particle size are removed therefrom by means of water scrubbing. The fine solids recovered from the tail gas scrubber, from the C2 product scrubber, and the Ca quench all recovered in the form of a water individual slurries are concentrated and introduced into the bottom of the desorber section via line 35.

During the passage of the adsorbent through adsorption-desorption cycle, some of the adsorbent becomes deactivated due to the collection thereon of impurities, such as heavy hydropolymers, etc., which were contained in primary adsorpthe components of the stream during the cycle. In order to reactivate the deactivated adsorbent a portion of in the neighborhood of 1000 to 1600 F. During this heating treatment contaminants are removed from the adsorbent and passed overhead from the reactivator via line 36. The hot reactivated adsorbent is returned via line 33 to the bottom of the desorber section 01' the primary tower for use again in the adsorption cycle.

In the primary adsorption tower and in the sidestream adsorber the adsorbent is handled as a dense fluid bed of approximately 50200 micron average particle size. The particles possess considerable motion relative to each other and plates or packing are required in the tower in order to effect suificient countercurrent contact between solid and vapor. In one modification of the tower design the tower is supplied with perforated plates with simple standpipe overflows for the solid, the vapor passing upward through the plate perforations. Approximately 2 to 3 feet of dense bed and 2 feet of vapor disengaging space per plate are adequate for establishment of equilibrium between vapor and solid. To feed the auxiliary tower fluidized solid flows from the tower i through a standpipe into line i6 provided with a slide valve. A similar system is used for the return of the fluidized solids from vessel IE to rectifier section 3 via line 20.

The flow of adsorbent downwardly through the equipment has been described above. The fracas these vary with the nature of the feed and the nature of the adsorbent.

Referring again to the drawing a feed gas mixture containing hydrogen, methane, and C: hy drocarbons, ethane and ethylene, and Ca and higher hydrocarbons is supplied via line I to the gas at temperatures I bottom section of the absorber 2 at which point the carbon may have a temperature of about to 200 F. At this point a pressure preferably of about 1 to 7 atmospheres may exist.

temperature of the granular activated charcoal entering the top of the absorber is approximately 500 F. However, as the carbon gradually flows downwardly through the absorber section of the tower, it becomes progressively cooled by one or more coolers represented by the numeral 9. The unadsorbed gas passing upwardly through the adsorber section 2 carries out any steam being brought down with the hot carbon as it flows contains only adsorbed C2 much smaller amounts of methane. In the sidestream adsorber 15 this carbon is refluxed with vapors entering the bottom thereof via line H. The sidestream adsorber acts as a rectification zone where there is displaced any methane carried into the vessel with the carbon via line Hi. This methane is displaced and passes upwardly through the top of the sidestream adi9 for return to the The charcoal passing below the feed 5 into I rectifier section 3 is treated by rising C2 and higher hydrocarbon vapors which are desorbed by heating the charcoal by means of heater 2i in desorber 4 to a-temperature of about 400 to 550 contain a mixture of C2 and Cs hydrocarbons with larger or smaller amounts of methane depending upon the point of withdrawal. Any hydrogen present in the feed gas will be removed along with methane in lines l and IS in the above described operation. The process as described above is also applicable to the treatment of other hydrocarbon mixtures and other gas or vapor mixtures in general containing 3 or more components of different degress of adsorption.

It is preferred to remove carbon dioxide from the hydrocarbon feed by scrubbing before the feed enters the adsorption zone. If it is not removed it will appear in the products from the adsorption zone. In most instances hydrogen sulfide to some extent is also present in the hydrocarbon feed gas and its removal is also desired since it would appear in the C: and Cs product streams. Both contaminants are simultaneously removed by scrubbing, for example, in a Girbotol unit.

Operating conditions-equipment size, etc.

An example of suitable operating conditions for conducting the process as described above with particular reference to the drawing is as follows:

The tower l is 12 feet in diameter, preferably expanded to 15 feet in the desorber section, and 120 feet high. The side-stream tower i5 is 20 feet high and 6 feet in diameter. Charcoal is supplied to primary tower l at the rate of 500 tons per hour, 14 tons being diverted through line 30 for reactivation in reactivator 3|. About 350 standard cubic feet per second of a feed gas are supplied through line 5 at a temperature of 120 to 160 F., and at a pressure of 6 atmospheres, the column being operated to take only the necessary pressure drop without disturbance of the steady charcoal fiow in both the primary tower and the side-stream tower. Thus tower -l is operated at a top pressure of about 73 p. s. i. g. and a bottom pressure of about 80 p. s. i. g. and the sidestream tower i5 is maintained at '75 p. s. i. g. pressure. The coolers operate so that the temperature of the carbon immediately above the gas feed point is approximately 100 to 200 F., and the charcoal is heated by heater 2| to a temperature in the range of 400 to 550 F. Thus a temperature of approximately 180 F. is provided in the rectifier 3 at a point about where the sidestream vapor is removed via line H. Substantially all of the stripping steam therefore is removed via line 23 with the heavier hydrocarbon product.

The solids heater which serves to desorb the product plus reflux vapor is designed with perforated plates, bubble-cap plates, or packing, etc., such that staging is achieved during the transfer ofheat and less surface is required due to the improved average temperature difference. The perforated plates are fitted over vertical tubes which contain the heating medium (hot gases, condensing steam or Dowtherm, etc.) and the solids overflow from stage to stage on the shell side of the exchanger via standpipes. Steam or other stripping vapor passes upward through the unit, and serves to maintain the solid particles in a turbulcntly fluidized condition. Heat transfer coeflicients exhibited by dense beds of fluidized solids are much higher than those realized with nonfiuidized solid beds and therefore surface is saved. The solids cooler (dense fluidized solid on the shell side and the cooling water on the tube side) is also designed with packing or perforated plates fitting over the cooling tubes in 7a duced at low pressures; to

8 order to stage the solid and minimize the heat exchange surface requirement.

The adsorption towers are designed with perforated plates equipped with standpipe overflows for the solids in order to obtain stepwise contact between solid and gas. Packing or bubble-cap plates can also be used. The charcoal inventory in a tower of a given diameter and height is very much smaller when the solid is fluidized than when it is handled as a moving bed. The adsorption tower may be reduced in cross-section below the point of gas feed entry, due to the smaller gas rate in this section, and thereby more uniform gas velocity is obtained throughout the tower. The reduced tower cross-section also corresponds to reduced adsorbent inventory and therefore an appreciable saving in initial plant investment is realized.

The quench tower, which serves primarily to remove steam and sensible heat from the product vapor, is also made to perform the added duty of recovering final traces of entrained solids (which are subsequently recycled to the process as a thickened slurry in water) and therefore the need for electrical precipitators or dust filters is eliminated.

In using fluidized solids of very small particle size, the time of contact required between solid and vapor in the adsorber and exchanger stages is reduced and therefore the solids inventory and initial investment are reduced. Also pressure drops in the towers, exchangers, and gas lifts are reduced and thus a saving in the work of gas compression is realized.

It is recognized that all of the gas streams described above which are withdrawn from contact with the carbon will contain appreciable quantities of dust or fines and that suitable dust separators are included in such gas lines before the gas is passed through the exit flow control valves. Suitable condensers and separators may also be provided where the gas contains readily condensible materials such as C4 or heavier hydrocarbons, water vapor and the like. These have been omitted from the drawing for the purpose of simplicity.

Application of the adsorption process The invention is generally applicable to fractionation processes of the type illustrated above, involving selective adsorption of one or more components from a mixture containing other components which are more and less readily adsorbed. In such operations it may be used to separate hydrocarbon mixtures into fractions of any desired boiling range or chemical structure by suitable selection of adsorbents and stripping agents in conformity with chromatographic principles. For example, parafilns, naphthenes, olefins, diolefins and aromatics may be obtained as separate fractions from mixture of two or more of these classes of hydrocarbons with a silica gel adsorbent used in an adsorption process as described above in one or more stages according to the number of fractions to be separated. Similarly, organic apors of different degrees of polarity on any suitable solid adsorbents.

The process is particularly applicable tothe recovery of ethane and Ca hydrocarbons from refinery fuel gas; to the recovery of light ends from low pressure catalytic cracking gases; to the recovery of hydrocarbons and oxygenated compounds from hydrocarbon synthesis gas prothe separation of deumay also be separated by selective adsorption terium from hydrogen, methane from nitrogen, and to the recovery of acetylene from the gases of the Wulfi' process.

What is claimed is:

1. An improved intermediate component B passing a. vaporous stream tower. passing a stream of adsorbent containing methane and C2 hydrocarbons but substantially free of Ca hydrocarbons from the adsorption secremoving a stream of C: hydrocarbons substan tially free of methane and C3 hydrocarbons from a center portion of the auxiliary tower.

mary tower.

4. A process 5. A process according to claim 2 in which the hydrocarbon gas mixture also contains C4 hydrocarbons which are removed with the C3 hydrocarbons from the rectifier section of the primary tower.

HAROLD- w. SCHEELINE.

REFERENCES CITED The following references are of record in the file 01' this patent:

UNITED STATES PATENTS Number Name Date 1,422,007 sod July 4, 1922 2,335,009 Hollaway 'Nov. 23, 1943 2,495,842 Gilliland Jan. 31, 1950 OTHER REFERENCES A. I. Ch. E. Transactions, vol. 42, #4, August 25, 1946, pages 665-880, "Hypersorption Process."

Portion of an auxiliary Clyde H. 0. Berg. 

